Method for the separation of chemically modified rosin alcohols into components



Patented Nov. 4, 1941 METHOD FOR- THE SEPARATION OF CHEM- ICALLYMODIFIED ROSIN ALCOHOLS INTO COMPONENTS Joseph N. Borglin, Wilmington,DeL, assignor to Hercules Powder Company, Wilmington, DeL, a.corporation of Delaware No Drawing. Application September 28, 1939,

, Serial No. 296,946

16 Claims.

This invention relates to a method for the separation of alcoholderivatives of chemically modified rosins into components, and moreparticularly the separation of alcohol derivatives of chemicallymodified rosins into components by treatment with a selective solvent.

Due to the complexity of the chemical structure of rosin, treatments forthe production of chemical modifications practically always result inproducts which are mixtures of two or more chemical compounds. Theproduct may contain unchanged rosin or the rosin may be converted intotwo or more different materials, or both. Theesterification of such amodified product produces a modified rosin ester which, similarly, is amixture of chemically different esters. Likewise, esterification ofrosin and then treatment to produce chemical modification, gives aproduct which is a mixture of chemically difierent esters. Similarly,treatment of the modified rosin to produce an alcohol derivativethereof, gives an alcohol which is a mixture of the resin alcoholsderived from the components of the modified rosin material. Likewise,treatment of rosin to produce an alcohol and then chemical modificationof the rosin alcohol by the procedures utilized in chemically modifyingthe rosin produces a similar mixture of chemically difierent resinalcohols.

Thus, for example, the hydrogenation of rosin may result in a mixture ofunchanged rosin and dihydro-rosin. More ,complete hydrogenation resultsin a mixture of dihydro-rosin and tetrahydro-rosin. The production of aproduct which is entirely tetrahydro-rosin has so far proved impossible.The esterification of a hydrogenated rosin results in a mixture of rosinesters. Likewise, the hydrogenation of rosin esters results in a mixtureof ordinary rosin ester and dihydro-rosin ester or a mixture ofdihydrorosin ester and tetrahydro-rosin ester. Similar mixtures exist inthe alcohol derivatives of the hydrogenated rosin.

been developed, in spite of the fact that it has been fully realizedthat such separation would be of great value from a commercialstandpoint, as well as from a scientific standpoint.

Now, I have found that I can separate alcohol derivatives of chemicallymodified rosins into their components by a method which is relativelysimple, efiicient and adaptable to commercial operation. I accomplishthis by treating an alcohol derivative of chemically modified rosin witha substance selected from the group of substances now known to the artto be selective solvents for the visible and latent color bodies ofrosin.

The process in accordance with this invention consists of treating analcohol derivative of a modified rosin with a solvent which is aselective solvent for the color bodies of rosin, separating theselective solvent from the undissolved component of the alcoholderivative of the modified rosin and recovering the component of thealcohol derivative of the modified rosin dissolved therein, as, forexample, by evaporating the selective solvent. This process can berepeated as many times as necessary to produce the desired separation ofthe components.

In carrying out this method, the alcohol derivatives of the modifiedrosins may or may not be first dissolved in a solvent therefor which isimmiscible with the selective solvent which is used. Ordinarily, it willbe found convenient to use such a solvent, particularly if the alcoholderivative of the modified rosin treated is a solid at the temperatureof treatment. When it is desired to use a solvent for the alcoholderivative of the modified rosin, the procedure in accordance with thisinvention will consist of dissolving the alcohol'derivative of themodified rosin in the solvent, contacting the solution so formed with aselective rosin color body solvent immiscible therewith, separating thetwo solutions thus formed, and recovering a component of the alcoholderivative of the modified rosin from each solution as, for example, byevaporating the respective solvents, preferably under reduced pressure.This procedure may be repeated as many times as desired.

After separating the alcohol derivative of the modified rosin intocomponents by the above procedure, each component may be furtherpurified by crystallization from suitable solvents, fractionation underreduced pressure, contactingv with an absorbent such as, fullers earth,kieselguhr, activated carbon etc.

The alcohol derivative of a modified rosin which I may treat inaccordance with this invention may be an alcohol derivative of any rosinwhich has been treated to modify its chemical structure so that theresultant product is a mixture of two or more chemically differentsubstances. The hydrogenation of rosin in the presence of a suitablecatalyst according to methods known to the art produces such a modifiedrosin. The treatment of a hydrogenated rosin to produce an alcoholderivative, likewise, produces an alcohol which is a mixture of theresin alcohols derived from the different components of the hydrogenatedrosin as well as non-alcoholic impurities present. Similarly,hydrogenation of a rosin alcohol gives a mixture of two or morechemically different substances. The alcohol derived from hydrogenatedwood rosin, for example, may contain dihydroabietyl alcohol andtetrahydroabietyl alcohol among other constituents.

The polymerization of rosin to increase its molecular weight and meltingpoint by treatment with a polymerizing agent, for example, volatilemetal halides, as, boron trifluoride, zinc chloride, stannic chloride,aluminum chloride, ferric chloride; mineral acids, as, sulfuric acid,phosphoric acid; fullers earth; hydrogen fluoride; acid salts, as sodiumacid sulfate, etc.; metallic silicon; hydro fiuoro-boric acid; etc.,according to methods known to the art, produces such a modified rosin.The treatment of the polymerized rosin to produce an alcohol derivative,for example, hydrogenation, produces an alcohol which is a mixture ofthe resin alcohols derived from the different components of thepolymerized rosin aswell as non-alcoholic impurities present. Similarly,polymerization of a rosin alcohol gives a mixture of two or morechemically different substances.

Again, the treatment of rosin with a suitable catalyst, as, for example,a hydrogenation catalyst, as nickel, nickel chromite, platinum,palladium, etc., at an elevated temperature of, for example, from about150 C. to about 200 C. and without reaction between the rosin and anyadded substance, to produce an intraand intermolecular rearrangementwithin the hydrocarbon nucleus of the rosin with a reduction in theapparent unsaturation as disclosed in U. S. Patent No. 2,154,629, issuedApril 18, 1939, to Edwin E. Littmann produces a modified rosin which maybe used in the preparation of an alcohol derivativeto be treated inaccordance with this invention. Suchmodified rosins will hereinafter betermed Hyex rosins. The treatment of the Hyex rosin to produce analcohol derivative produces an alcohol which is a mixture of theresinalcohols derived from the different components of the Hyex rosin aswell as nonalcoholic impurities present. Similarly, Hyex treatment of arosin alcohol gives a mixture of two or more chemically differentsubstances.

The alcohol derivatives of modified rosins which I treat in accordancewith this invention may be the alcohol derivatives of modified rosinsproduced from any grade of wood or gum rosin which has been treated tomodify its chemical structure so that the modifiedrosin resulting is amixture of two or more chemically different materials. The alcoholderivatives of the modified rosins may be prepared from the modified.rosins in any suitable manner such as by hydrogenation of the modifiedrosin under conditions which are satisfactory 'for alcohol formation.Alternatively, a rosin alcohol may be produced from rosin or a rosinester by suitable hydrogenation treatment. and the resulting rosinalcohol submitted ,to a treatment which will effect a modification ofthe rosin nucleus of the rosin alcohol.

The selective solvent which I use in accordance with this invention maybe any of the various selective solvents for the visible and latentcolor bodies of rosins and rosin esters heretofore known. Thus, I mayuse furfural, furfuryl alcohol, a chlorohydrin, as, ethylenechlorohydrin, propylene chlorohydrin, etc., aniline, phenol, resorcinol,ethylene glycol, propylene glycol, butylene glycol, diethylene glycol,trimethylene glycol, glycerol, butyl glycerol, ethyl formate, methylacetate, methyl formate, methyl orthonitrobenzoate, methyl furoate,alkyl formate, monoacetin, diacetin, triacetin, ethylene glycolmonoacetate, methanol, hydroxyl alkyl amine, as triethanolamine, asolution of oxalic acid in water or in methanol, ethanol or other loweraliphatic alcohol, ethylene glycol monoethyl ether, or other immiscibleglycol ether, ethylene glycol monoacetate, or other immiscible glycolester, methyl thiocyanate, ethyl thiocyanate, acetonitrile, acetic acid,acetic anhydride, p-chloroaniline, resorcinol plus hydrosulphite,ethylene glycol diacetate, glycerol diacetate, resorcinol monoacetate,resorcinol diacetate, phenyl acetate, furfuryl acetate, ethylidinediacetate, n-propyl furoate, ethyl glycolate, methyl citrate, ethyltartrate, ethyl malonate, methyl maleate, dimethyl phthalate, benzylformate, monobutyrin, ethyl carbonate, methyl lactate, diethyl oxalate,methyl adipate, hydroxyhydroquinone triacetate, methyl chlorocarbonate,propylene glycol, monoacetate, hydroquinone diacetate, catecholmonoacetate, guaiacyl acetate, methyl glutarate, ethyl oxalate, benzylacetate, diethyl glutacoate, ethyl lactate, diethyl phthalate, ethylanisate, methyl salicylate, methyl cinnamate, methyl mandelate, methylacrylate, ethyl oxamate, methyl succinate, ethyl propiolate, ethylmalate, methoxy-benzaldehyde, guaiacol, anisidin, nitroanisol,dichloroethyl ether, methoxy aceticacid, methoxybenzyl alcohol, liquidsulfur dioxide, nitromethane, etc., or mixtures of such refining agentswhich are chemically non-reactive, etc.

The solvent in which I may dissolve the alcohol derivative of themodified rosin before contacting it with a selective solvent may be anysolvent for the alcohol derivative of the modified rosin which isimmiscible and non-reactive with the selective solvent used. Thus, I mayuse a petroleum hydrocarbon solvent, such as, for example, gasoline,petroleum ether, a normally gaseous petroleum hydrocarbon held in liquidphase by elevated pressure, low temperature, or both. The concentrationof the alcohol derivative of the modified rosin in such a solution maybe within the range of about 5% to about by weight, and desirably withinthe range of about 15% to about 30% by weight.

The temperature at which the process in accordance with my invention maybe carried out is dependent upon the selective solvent employed and willbe within the range of about 40 C. to about +60 C. In any case thetemperature used will be such that the selective solvent is a liquidunder the pressure used.

In the embodiment of my process in which an alcohol derivative of achemically modified rosin is dissolved in a solvent therefor before itis contacted with a selective solvent, the solution so formed may have aconcentration within the range of about 5% to about 40%, by weight.Usually I prefer to use a solution having a concentration within therange of about 10% to about 25% by weight.

The number of washes employed in my process may be varied in accordancewith the results desired, and it will be appreciated that the greaterthe number of washes given the sharper will be the separation of thecomponents of the alcohol derivative of the chemically modified rosintreated.

As illustrations of the practical adaptation of the method in accordancewith this invention, I may cite the following:

EXAMPLE I Three portions of a 20% solution of dihydroabietyl alcohol ingasoline of 50 grams each were counter-currently washed with methylthiooy- 1anate at C., so that each gasoline solution received fivewashes with 10 cc. portions of methyl thiooyanate. The three refinedgasoline solutions and the combined thiooyanate solutions wereevaporated under reduced pressure to recover the dissolved fractions.The analyses and yields of these fractions of the dihydroabietyl alcoholare given in Table 1.

Table 1 Weight Hydroxyl Alcohol recovered D. H. A.

Per cent Per cent Gra 7 -8 Original dihydroabietyl alcohol. 4. 75Dihydroabietyl alcohol from gas.

50]. #1 4. 4 -13 0.7 Dihydroabietyl alcohol from gas.

sol. #2 4. 65 60 2.0 Dihydroabietyl alcohol from gas.

.501. #3 4. 7 80 11.8 Dihydroabietyl alcohol combined methyl thiooyanates01 4. 8 91. 12. 3

An inspection of the data of Table 1 shows that the original sample ofdihydroabietyl alcohol was 81% alcohol, while the fraction recoveredfrom the combined methyl thiooyanate solution was 91.5% dihydroabietylalcohol. As compared with this the fraction recovered in the No. 1gasoline solution was only 75% dihydroabietyl alcohol. Thus, thetreatment in accordance with this invention definitely concentrated thealcoholic portion of the original dihydroabietyl alcohol in the methylthiooyanate fraction.

EXAMPLE 11 Three portions of 100 grams each of a 20% solution ofdihydroabietyl alcohol in gasoline were washed counter-currently withaniline at '0" C., so that each gasoline solution received five washeswith cc. portions of aniline. The three refined gasoline solutions andalsothe combined aniline solutions were evaporated under reducedpressure to recover the dissolved products. The analyses and yields ofthese products are given in Table 2 which follows:

An examination of the above, data shows that aniline, like the methylthiooyanate of I the Example I selectively dissolves the dihydroabietylalcohol, yielding a fraction which was materially purer than theoriginal sample.

EXAMPLE III The alcohol derivative of Hyex rosin was prepared byhydrogenation of Hyex rosin over a copper chromite catalyst at atemperature of 270-300 C. and a maximum hydrogen pressure of 2800lbs/sq. in. Three portions of 160 grams each of a 25% solution of thealcohol in gasoline were counter-currently washed at room temperature(25 C.) with first a cc. portion of furfural, then a 50 cc. portionfollowed by a 30 cc. portion and four 25 cc. portions of furfural. Theresulting gasoline solutions and the combined furfural washes wereevaporated under reduced pressure to recover the components dissolved ineach. The

results obtained are given in Table 3.

Table 3 Refrac- Hy- Acid tive in droxnum- Grade Yield dex 20C. yl berPer- Per- Original alcohol from Hyex cent cent rosin 1. 5393 4. 2 5.0 HAlcohol from gas. sol. #1.'.. 1.5272 l-. 1 4. 1 WC 8 Alcohol from gas.sol. #2... 1. 5320 2. 5 5. 9 N 15. 2 Alcohol from gas. sol. #3--. 1.5353 3. 1 9.0 I 23. 2 Alcohol from combined furiural washes 1. 5467 4. 25. 4 D 53. 6

* By acetytation, corrected for acidity. v

A comparison of the characteristics of the above table shows that theoriginal alcohol has been separated into chemically different fractionsby the furfural wash.

I EXAMPLE IV Threeportions of 200 grams each of the 25% gasolinesolution of the alcohol derived from Hyex Table 4 Refrac- Hy- Acid tiveindroxnum- Grade Yield dex 20C. yl ber Per- Per- Origmal alcohol fromHyex cent cent rosin 1.5393 4. 2 5.0 H Alcohol from gas. sol. #1... l.5286 1.4 3.0 WW 6. 1 Alcohol from gas. sol. #2.-. 1. 5351 3.0 4. 6 WGl3. 2 Alcohol from gas. sol. #3... 1. 5370 3. 7 5. 1 N 19. 7 Alcoholfrom combined phenol washes 1.5426 ,4. 8 5. 2 H 61. 0

*By acetylation, corrected for acidity.

Inspection of the data of Table 4 shows that.

the original alcohol has been separated into different components havingdifferent characteristics. An alcohol of considerably higher purity Wasisolated from the combined phenol washes.

EXAMPLE V Three portions of 200 grams each of the 25% gasoline solutionof the alcohol derived from I-Iyrex rosin used in Example III werecountercurrently washed at room temperature (25 C.) first with a 100 cc.portion of methyl thiocyanate then with three successive 50 cc. portionsfollowed by two 30cc. portions of methyl thiocyanate. After each washthe solutions were cooled in an ice-bath to permit more completeseparation of the methyl thiocyanate layer. The gasoline solutions andthe combined methyl thiocyanate washes were evaporated under reducedpressure to recover the components dissolved in each. Thecharacteristics of the products recovered from each of the solutions areshown in Table 5.

By acetylation, corrected for acidity.

A comparison of the characteristics shown in Table 5 illustrates theseparation of the original alcohol into chemically different components.

EXAMPLE VI The alcohol derivative of polymerized rosin was prepared byhydrogenating a polymerized rosin which had been polymerized bytreatment with sulfuric acid. The hydrogenation was carried out with useof a copper chromite catalyst at a temperature of 275-300 C. at amaximum hydrogen pressure of 1900-2300 lbs/sq. in. Three portions of 140grams each of a 25% solution of the alcohol in gasoline werecounter-currently washed at room temperature (25 C.) with first a 50 cc.portion of furfural, then two 39 cc. portions, a 35 cc. portion andfinally three 25 cc. portions of furfural. The gasoline solutions andthe combined furfural wash solutions were evaporated under reducedpressure to recover the components dissolved in each. The resultsobtained The characteristics shown above demonstrate that the originalalcohol has been separated into components of chemically differentcharacteristics.

EXAMPLE VII Three portions of 140 grams each of the 25% gasolinesolution of the alcohol derivative of polymerized rosin used in ExampleVI were countercurrently washed at room temperature with first a 50 cc.portion of 85% aqueous phenol, then a 30 cc. portion, two 25 cc.portions and finally two 20 cc. portions of aqueous phenol. The threegasoline solutions and the combined phenol washes were evaporated underreduced pressure to recover the components dissolved in each. Theresults obtained are given in Table 7.

Table 7 Refrac- Acid tive Hyindex droxyl g Yleld 20 0.

Per- Per- Original alcohol from polymerized cent cent rosin 1. 5382 3. 334. 5 Alcohol from gas. sol. #1. 1. 5323 1. 1 19. 0 0. 5 Alcohol fromgas. sol. #2 1. 5357 2. 2 25. 5 16. 2 Alcohol from gas. sol. #3 1. 53542. 4 29. 5 17. 1 Alcohol from combined phenol washes 1. 5409 4. 6 57. 2

An examination of the above data shows that as a result of the phenolwashes the alcohol derived from polymerized rosin has been separatedinto components having chemically different characteristics.

EXAMPLE VIII Table 8 Refrac- Acid tlve v Hyindcx droxyl g held 20C.

Per- Per Original alcohol from polymerized cent cent rosin l. 5382 3. 334. 5 Alcohol from gas. sol. #1. l. 5332 1.6 28.0 0. 8 Alcohol from gas.sol. #2... 1. 5358 2. 5 34.0 19.0 Alcohol from gas. sol. #3 l. 5382 3.034. 5 20. 5 Alcohol from combined methyl thiocyanate washes 1. 5434 3. 433. 0 50. 7

The characteristics shown in Table 8 illustrate the separation of thealcohol derivative of polymerized rosin into components of chemicallydifferent characteristics by the methyl thiocyanate washes.

It will be understood that the above examples and details of operationare given by way of illustration only, and that the scope of myinvention as herein broadly described and claimed is in no way limitedthereby.

Where in the appended claims I have used the term chemically modifiedrosin alcohol it will be understood that I mean a rosin alcohol in whichthe rosin nucleus has undergone a chemical modification.

This application forms a continuation-in-part of my application, SerialNo. 160,725, filed August 24, 1937, entitled Method for the separationof chemically modified rosins and their esters into components, now U.S. Patent No. 2,191,306.

What I claim and desire to protect by Letters Patent is:

1. The method of separating a hydroabietyl alcohol into its components,which comprises dissolving the hydroabietyl alcohol ina petroleumhydrocarbon solvent, contacting the solution so formed with furfural,separating the furfural therefrom and recovering a component of thehydroabietyl alcohol from each of the resulting solutions by evaporatingthe solvent.

2 The method of separatirrg a chemically modified rosin alcohol in'whichthe rosin nucleus has undergone a chemical modification into itscomponents, which comprises dissolving the said chemically modifiedrosin alcohol in a solvent therefor, contacting the solution so formedwith a selective rosin color-body solvent immiscible with the saidsolution, separating the selective solvent therefrom and recovering acomponent of the chemically modified rosin alcohol from each of theresulting solutions.

3. The method of separating a chemically modified rosin alcohol in whichthe rosin nucleus has undergone a chemical modification into itscomponents, which comprises dissolving the said chemically modifiedrosin alcohol in a solvent therefor, contacting the solution so formedwith a selective rosin color-body solvent immiscible with the saidsolution, separating the selective solvent therefrom and recovering acomponent of the chemically modified rosin alcohol from each of theresulting solutions by evaporating the solvent.

4. The method of separating a chemically modified rosin alcohol in whichthe rosin nucleus has undergone a chemical modification into itscomponents, which comprises dissolving the said chemically modifiedrosin alcohol in a petroleum hydrocarbon solvent, contacting thesolution so formed with a selective rosin color-body solvent immisciblewith the said solution, separating the selective solvent therefrom andrecovering a component of the chemically modified rosin alcohol fromeach of the resulting solutions by evaporating the solvent.

5. The method f separating a chemically modified rosin alcohol in whichthe rosin nucleus has undergone a chemical modification into itscomponents, which comprises dissolving the said chemically modifiedrosin alcohol in a solvent therefor which is immiscible with furfural,contacting the solution so formed with furfural, separating the furfuraltherefrom and recovering a component of the chemically modified rosinalcohol from each of the resulting solutions by evaporating the solvent.

6. The method of separating a chemically modified rosin alcohol in whichthe rosin nucleus has undergone a chemical modification into itscomponents, which comprises dissolving the said chemically modifiedrosin alcohol in a solvent therefor which is immiscible with phenol,contacting the solution so formed with phenol, separating the phenoltherefrom and recovering a com ponent of the chemically modified rosinalcohol from each of the resulting solutions by evaporating the solvent.

7. The method of separating a chemically modified rosin alcohol in whichthe rosin nucleus has undergone a chemical modification into itscomponents, which comprises dissolving the said chemically modifiedrosin alcohol in a solvent therefor which is immiscible with alkylthiocyanates, contacting the solution so formed with an alkylthiocyanate, separating the alkyl thiocyanate therefrom and recovering acomponent of the chemically modified rosin alcohol from each of theresulting solutions by evaporating the solvent.

8. The method of separating a chemically modified rosin alcohol in whichthe rosin nucleus has undergone a chemical modification into itscomponents, which comprises dissolving the said chemically modifiedrosin alcohol in a petroleum hydrocarbon solvent, contacting thesolution so formed with vfurfural, separating the furfural therefrom andrecovering a component of the chemically modified rosin alcohol fromeach of thetresulting solutions by evaporating the sol- Ven 2 9. Themethod of separating a hydrogenated rosin alcohol into its componentswhich comprises dissolving the hydrogenated rosin alcohol in a petroleumhydrocarbon solvent, contacting the solution so formed with furfural,separating the furfural therefrom and recovering a component of thehydrogenated rosin alcohol from each of the resulting solutions byevaporating the solvent.

10. The method of separating a chemically modified rosin alcohol inwhich the rosin nucleus has undergone a chemical modification into itscomponents, which comprises dissolving the said chemically modifiedrosin alcohol in a petroleum hydrocarbon solvent, contacting thesolution so formed with phenol, separating the phenol therefrom andrecovering a component of the chemically modified rosin alcohol fromeach of the resulting solutions by evaporating the solvent.

11. The method of separating a hydrogenated rosin alcohol into itscomponents which comprises dissolving the hydrogenated rosin alcohol ina petroleum hydrocarbon solvent, contacting the solution so formed withphenol, separating the phenol therefrom and recovering a component ofthe hydrogenated rosin alcohol from each of the resulting solutions byevaporating the solvent.

12. The method of separating a chemically modified rosin alcohol inwhich the rosin nucleus has undergone a chemical modification into itscomponents, which comprises dissolving the said chemically modifiedrosin alcohol in a petroleum hydrocarbon solvent, contacting thesolution so formed with an alkyl thiocyanate, separating the alkylthiocyanate therefrom and recovering a component of the chemicallymodified rosin alcohol from each of the resulting solutions byevaporating the solvent.

13. The method of separating a hydrogenated rosin alcohol into itscomponents which comprises dissolving the hydrogenated rosin alcohol ina petroleum hyrocarbon solvent, contacting the solution so formed withan alkyl thiocyanate, separating the alkyl thiocyanate therefrom andrecovering a component of the hydrogenated rosin alcohol from each ofthe resulting solutions by evaporating the solvent.

14. The method of separating a hydroabietyl alcohol into its components,which comprises dissolving the hydroabietyl alcohol in a petroleumhydrocarbon solvent, contacting the solution so formed with phenol,separating the phenol therefrom and recovering a component of thehydroabietyl alcohol from each of the resulting solutions byevaporating'the solvent.

15. The method of separating a hydroabietyl alcohol into its components,which comprises dissolving the hydroabietyl alcohol in a petroleumhydrocarbon solvent, contacting the solution so formed with an alkylthiocyanate, separating the alkyl thiocyanate therefrom and recovering acomponent of the hydroabietyl alcohol from each of the resultingsolutions by evaporating the solvent.

16. The method of separating a chemically modified rosin alcohol inwhich the rosin nucleus has undergone a chemical modification into itscomponents, which comprises dissolving the said chemically modifiedrosin alcohol in a solvent therefor, contacting the solution so formedcountercurrently with a selective rosin colorbody solvent immisciblewith the said solution, separating the selective solvent therefrom andrecovering a component of the chemically modified rosin alcohol fromeach of the resulting solutions by evaporating the solvent.

JOSEPH N. BORGLIN.

